Composition, production method for composition, and production method for unsaturated compound

ABSTRACT

The composition comprises a compound (A) represented by general formula (1) and a compound (B) represented by general formula (2), and comprises 0.00002 to 2.0 parts by mass of the compound (B) with respect to 100 parts by mass of the compound (A),
 
(R 1 —COO) n —R 2 —(NCO) m   (1)
 
(R 1 —COO) n —R 2 —NHC(═O)NH—R 2 —(OCO—R 1 ) m   (2)
 
wherein in general formulae (1) and (2), R 1  is an ethylenically unsaturated group having 2 to 7 carbon atoms; R 2  is a (m+n)-valent hydrocarbon group having 1 to 7 carbon atoms and optionally contain an ether group; R 1  and R 2  in the general formula (1) are the same as R 1  and R 2  in the general formula (2); and n and m each represent an integer of one or two.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2019/032135 filed Aug. 16, 2019, claiming priority based onJapanese Patent Application No. 2018-154146 filed Aug. 20, 2018.

TECHNICAL FIELD

The invention is related to a composition containing an unsaturatedisocyanate compound, a method of producing the composition, and a methodof producing an unsaturated compound.

This application claims priority under Japanese Patent Application No.2018-154146 filed Aug. 20, 2018, the contents of which are incorporatedherein by reference.

BACKGROUND TECHNOLOGY

Conventionally, a unsaturated compound such as an unsaturated urethanecompound, an unsaturated thiourethane compound, an unsaturated ureacompound, and an unsaturated amide compound, is produced by reacting anunsaturated isocyanate compound with a compound having active hydrogen(the compound having functional group having active hydrogen). Theunsaturated compound thus produced is used in various applications.

For example, there is an unsaturated urethane compound produced byreacting 2-methacryloyloxyethyl isocyanate (Hereinafter, this may bereferred to as “MOI”. An example of a specific product is “KarenzMOI(registered trademark)”.) which is an unsaturated isocyanate compoundwith a polyalkylene glycol which is a compound having a hydroxyl group.There are known methods for producing the unsaturated isocyanatecompound, such as a method for reacting an amine having an ethylenicdouble bond with phosgene to decompose the amine by heating (forexample, see Patent Document 1). The unsaturated urethane compound isproposed to be used as a material for contact lenses (for example, seePatent Document 2), a material for solid solvents of polymer solidelectrolytes (for example, see Patent Document 3.), and a material forimmobilizing biological materials (for example, refer to PatentDocuments 4 and 5).

Further, Patent Document 6 discloses an unsaturated urea compoundobtained by reacting MOI with an organopolysiloxane having amino groupsat both ends of the molecule. Patent Document 6 discloses using theunsaturated urea compound as a material for a radiation-curable adhesiveorganopolysiloxane composition.

Patent Document 7 discloses a urethane acrylate synthesized by reactingan unsaturated isocyanate compound such as MOI with a product obtainedby reacting a dimer diol with a polyisocyanate. Further, Patent Document7 discloses a curable composition containing the urethane acrylate.

Examples of the unsaturated isocyanate compound used as a material ofthe unsaturated compound include acryloyloxyethyl isocyanate(Hereinafter, this may be referred to as “AOI”. An example of a specificproduct is “KarenzAOI (registered trademark)”.) and methacryloylisocyanate (Hereinafter referred to as “MAI”.) in addition to MOI. MOI,AOI, and MAI are industrially manufactured, commercially available, andreadily available.

MOI is synthesized by the reaction of isopropenyloxazoline or2-aminoethyl methacrylate hydrochloride with phosgene. AOI issynthesized by the reaction of 2-vinyloxazoline or 2-aminoethylacrylatehydrochloride with phosgene. MAI is synthesized by the reaction ofmethacrylic amide with oxalyl chloride.

The unsaturated isocyanate compound synthesized as described aboveincludes impurities such as by-products and catalyst residues. For thisreason, after the unsaturated isocyanate compound is synthesized, anoperation for removing impurities to increase the purity is generallyperformed (for example, see Patent Documents 8 and 9.).

The synthesized unsaturated isocyanate compound is conventionallydetermined by various methods. Specifically, there are a method forconfirming the appearance of the unsaturated isocyanate compound such asthe presence or absence of turbidity and hue, a method for confirmingthe purity of the unsaturated isocyanate compound by using gaschromatography, a method for confirming the hydrolyzable chlorinecontent in the unsaturated isocyanate compound by potentiometrictitration, and a method for confirming a soluble impurity in theunsaturated isocyanate compound by using gel permeation chromatography(GPC) (See, for example, Patent Document 10.).

Generally, in order to stably transport and store the unsaturatedisocyanate compound, a polymerization inhibitor is added to theunsaturated isocyanate compound. As the polymerization inhibitor,hydroquinone or the like is used and is added at a concentration ofseveral tens to several hundred ppm. For example, Patent Document 7discloses that, when an unsaturated urethane compound is synthesizedusing an unsaturated isocyanate compound, a polymerization inhibitor isadded in an amount of 0.01 to 10 parts by mass based on 100 parts bymass of the total weight components.

PATENT DOCUMENTS

-   [Patent Document 1] U.S. Pat. No. 2,821,544-   [Patent Document 2] Japanese Patent Laid-Open No. H06-322051-   [Patent Document 3] Japanese Patent Laid-Open No. H06-187822-   [Patent Document 4] Japanese Patent Laid-Open No. S60-234582-   [Patent Document 5] Japanese Patent Laid-Open No. S60-234583-   [Patent Document 6] Japanese Patent Laid-Open No. H06-184256-   [Patent Document 7] WO 2011/074503-   [Patent Document 8] Japanese Patent No. 4273531-   [Patent Document 9] Japanese Patent No. 4823546-   [Patent Document 10] Japanese Patent Laid-Open No. 2007-8828

NON-PATENT DOCUMENTS

-   [Non-Patent Document 1] CMC Technical Library “Polymer degradation    mechanism and stabilization technology” CMC Publishing Co., Ltd.    (Issued on 2005/04) Page 168, FIG. 5.

SUMMARY OF THE INVENTION

Conventional unsaturated isocyanate compounds may cause unexpectedviscosity increases or gelation during storage and/or transport, eventhough there is no significant difference in quality by usingconventional determination methods. Therefore, it has been required toimprove the stability during storage.

In addition, the conventional unsaturated isocyanate compound does notshow a large difference in quality by using the conventionaldetermination method, but when the unsaturated compound is produced byusing the same, the viscosity of the reaction product is sometimesrapidly increased or gelatinized during production. Therefore, it hasbeen required to improve the stability in use.

In order to improve the storage stability and the utilization stabilityof the unsaturated isocyanate compound, a sufficient amount of apolymerization inhibitor may be added to the unsaturated isocyanatecompound.

However, when a large number of polymerization inhibitors are added toan unsaturated isocyanate compound, a colored component caused by thepolymerization inhibitor is easily generated together with theunsaturated compound when the unsaturated compound is produced using theunsaturated isocyanate compound as a raw material (for example, seeNon-patent Document 1.). Therefore, the produced unsaturated compoundmay be colored.

An object of the present invention is to provide a composition excellentin stability during storage and stability during use, and a method ofproducing the composition.

Means to Solve the Problem

In order to solve the above problems, the present inventors havediligently investigated. As a result, it was found that a compoundhaving a specific structure (hereinafter referred to as “specificcompound”) contained as an impurity in the unsaturated isocyanatecompound after purification is one of the causes of deterioration of thestorage stability and the stability during use of the unsaturatedisocyanate compound. Further, the inventors of the present inventionhave repeatedly studied and found that the concentration of the specificcompound in the unsaturated isocyanate compound has a correlation withthe viscosity increase and the occurrence of gelation of the unsaturatedisocyanate compound during storage.

However, a purification process for removing the specific compound fromthe unsaturated isocyanate compound has not been known. Therefore, thepresent inventors have studied a purification process for removing thespecific compound from an unsaturated isocyanate compound. As a result,it was found that the specific compound can be removed from theunsaturated isocyanate compound by purification by using a distillationprocess at a reflux ratio of 2.0 to 4.0, a pressure of 1.0 to 10.0 kPa,and a distillation temperature of 90 to 140° C.

Further, the inventors examined the viscosity increase and gelationduring storage of the unsaturated isocyanate compound purified by thedistillation process at the reflux ratio, the pressure and thedistillation temperature. As a result, it has been found that theviscosity increase and gelation can be suppressed by setting theconcentration of the specific compound in the unsaturated isocyanatecompound to 2.0 parts by mass or less with respect to 100 parts by massof the unsaturated isocyanate compound.

The inventors have also found that even if the specific compound in theunsaturated isocyanate compound is sufficiently removed by thedistillation process, the specific compound in the unsaturatedisocyanate compound increases when the purified product obtained by thedistillation process comes into contact with water. Further, the presentinventors have found that the increase of the specific compound in thecomposition after production can be effectively suppressed by performinga vacuum breaking step in which dry nitrogen gas having a dew point of−30° C. or lower is supplied into the distillation apparatus after thedistillation process and the pressure in the distillation apparatus isreturned to the atmospheric pressure, and a filling step in which thepurified product in the distillation apparatus after the distillationprocess is stored in a container and the gas phase portion in thecontainer is filled with dry nitrogen gas having a dew point of −30° C.or lower.

In other words, the present invention relates to the following matters.

The composition according to the first embodiment of the presentinvention is the following composition.

[1] A composition comprising a compound (A) represented by generalformula (1) and a compound (B) represented by general formula (2);

the composition contains 0.00002 to 2.0 parts by mass of the compound(B) with respect to 100 parts by mass of the compound (A).(R₁—COO)_(m)—R₂—(NCO)_(m)  (1)(R₁—COO)_(n)—R₂—NHC(═O)NH—R₂—(OCO—R₁)_(m)  (2)

(In general formulae (1) and (2), R₁ is an ethylenically unsaturatedgroup having 2 to 7 carbon atoms. R₂ a (m+n)-valent hydrocarbon grouphaving 1 to 7 carbon atoms and optionally comprises an ether group. R₂may contain an ether group. R₁ and R₂ of the general formula (1) are thesame as R₁ and R₂ of the general formula (2). n and m are integers of 1or 2.)

The composition of the first embodiment of the present invention alsopreferably has the following features [2] to [5]. These features arepreferably combined.

[2] The compound (A) may be at least one compound selected from thegroup consisting of 2-methacryloyloxyethyl isocyanate,2-(isocyanatoethyloxy) ethyl methacrylate, 2-acryloyloxyethylisocyanate, 2-(isocyanatoethyloxy) ethyl acrylate, and1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[3] The content of the compound (A) may be 95.0% by mass or more.

[4] The content of the compound (A) may be from 97.0% by mass to 99.9%by mass.

[5] As an additive, the composition may further contain any one selectedfrom the group consisting of the group consisting of hydroquinone,methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol,2,6-di-tert-butyl-4-methylphenol (BHT), and phenothiazine.

The second embodiment of the present invention is a method of producingthe following composition.

[6] The method includes a step of producing a mixture which comprises acompound (A) represented by general formula (1) and a compound (B)represented by general formula (2) and which comprises more than 2.0parts by mass of the compound (B) with respect to 100 parts by mass ofthe compound (A); and

purifying the mixture by a distillation process at a reflux ratio of 2.0to 4.0, a pressure of 1.0 to 10.0 kPa and a distillation temperature of90 to 140° C.,

wherein the purifying step comprises

a vacuum breaking step of supplying dry nitrogen gas having a dew pointof −30° C. or lower into a distillation apparatus after distillationprocess and returning the pressure in the distillation apparatus toatmospheric pressure, and

a filling step of storing the purified product in the distillationapparatus after the distillation process in a container and filling thegas phase portion in the container with dry nitrogen gas having a dewpoint of −30° C. or lower.(R₁—COO)_(n)—R₂—(NCO)_(m)  (1)(R₁—COO)_(n)—R₂—NHC(═O)NH—R₂—(OCO—R₁)_(m)  (2)

(In general formulae (1) and (2), R₁ is an ethylenically unsaturatedgroup having 2 to 7 carbon atoms. R₂ a (m+n)-valent hydrocarbon grouphaving 1 to 7 carbon atoms and optionally comprises an ether group. R₂may contain an ether group. R₁ and R₂ of the general formula (1) are thesame as R₁ and R₂ of the general formula (2). n and m are integers of 1or 2.)

The method of producing the composition according to the secondembodiment of the present invention also preferably has the followingfeatures (7) to [10]. It is also preferable to combine them.

[7] In the composition obtained by the purifying step, a content of thecompound (B) with respect to 100 parts by mass of the compound (A) is0.00002 to 2.0 parts by mass.

[8] R₁ is CH₂═C(CH₃)— or a vinyl group in the general formulae (1) and(2).

[9] The dry nitrogen gas supplied in the vacuum breaking step and thedry nitrogen gas filled in the filling step have a dew point of −70° C.or higher.

[10] When performing the distillation process in the purifying step, themethod may include a step of adding, as an additive to the mixture, anyone selected from the group consisting of hydroquinone,methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol,2,6-ditert-butyl-4-methylphenol (BHT), and phenothiazine before startingto heat the mixture.

A third embodiment of the present invention is a method of producing thefollowing unsaturated compounds.

[11] A method of producing an unsaturated compound, comprising the stepsof: mixing the composition described in [1] or [2] with a compoundhaving active hydrogen; and reacting the compound (A) contained in thecomposition with the compound having active hydrogen to obtain areaction product.

It is also preferable that the producing method according to the thirdembodiment of the present application has the following features [12] to[15]. These features are preferably combined.

[12] The compound having the active hydrogen is an alcohol, a thiol, anamine or a carboxylic acid.

[13] The reaction product may be an unsaturated urethane compound, anunsaturated thiourethane compound, an unsaturated urea compound, or anunsaturated amide compound.

[14] The reaction product may be any one selected from the groupconsisting of 2-butanone oxime-O-(carbamoylethyl-2-methacrylate),2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, 2-butanoneoxime-O-(carbamoylethyl-2-acrylate), and2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl acrylate.

[15] The reaction temperature at which the compound (A) contained in thecomposition is reacted with the compound having the active hydrogen is−10 to 100° C.

Effect of the Invention

The composition comprises a compound (A) represented by general formula(1) and a compound (B) represented by general formula (2), wherein withrespect to 100 parts by mass of the compound (A), 0.00002 to 2.0 partsby mass of the compound (B) are contained. Therefore, unexpectedviscosity increase and gelation of the composition unlikely occur duringstorage and transportation, and stability during storage is excellent.The composition of the present invention unlikely causes a rapidincrease in viscosity or gelation of a reaction product generated duringproduction when an unsaturated compound is produced by using thecomposition, and is excellent in stability in use.

The composition of the present invention is excellent in stabilityduring storage and stability during use. Therefore, it is not necessaryto contain a large amount of a polymerization inhibitor which produces acolored component. Therefore, it is possible to prevent the unsaturatedcompound produced by using the composition of the present invention frombeing colored by the coloring component caused by the polymerizationinhibitor.

The method of producing the composition which contains more than 2.0parts by mass of the compound (B) with respect to 100 parts by mass ofthe compound (A), by purifying the mixture by a distillation process ata reflux ratio of 2.0 to 4.0, a pressure of 1.0 to 10.0 kPa, and adistillation temperature of 90 to 140° C. to obtain a purified productcontaining 0.00002 to 2.0 parts by mass of the compound (B) with respectto 100 parts by mass of the compound (A). Accordingly, the compositionof the present invention, from which the compound (B) affecting thestability during storage and affecting the stability during use issufficiently removed, can be produced in high yield.

In the method of producing the composition, the purifying step comprisesa vacuum breaking step of supplying dry nitrogen gas having a dew pointof −30° C. or lower into a distillation apparatus after the distillationprocess and returning the pressure in the distillation apparatus toatmospheric pressure, and a filling step of storing the purified productin the distillation apparatus after the distillation process in acontainer and filling a gas phase portion in the container with drynitrogen gas having a dew point of −30° C. or lower. Therefore, thecompound (A) in the purified product after the distillation process isunlikely brought into contact with water, and the compound (B) isunlikely increased in the composition after production. Therefore,according to the method of producing the composition of the presentinvention, a composition having good stability during storage andstability during use can be obtained.

The method of producing the unsaturated compound includes steps ofmixing the composition of the invention with a compound having activehydrogen and reacting the compound (A) contained in the composition withthe compound having active hydrogen to obtain a reaction product. In themethod of producing the unsaturated compound of the present invention,since the composition used as a material contains 0.00002 to 2.0 partsby mass of the compound (B) with respect to 100 parts by mass of thecompound (A), rapid increase in viscosity or gelation of the reactionproduct is unlikely generated during production, and excellentproductivity is obtained.

MODE FOR CARRYING OUT THE INVENTION

Preferred examples of the present invention will be described below.

It should be noted that the following examples are specificallydescribed for better understanding of the purpose of the invention, andthe invention is not limited to these examples unless otherwisespecified. Within the scope of the present invention, amounts, types,ratios, numbers, locations, and the like may be omitted, changed,replaced, and/or added as needed.

The pressure described herein is an absolute pressure.

“Composition”

The composition of this embodiment contains an unsaturated isocyanatecompound. The composition of this embodiment comprises a compound (A)represented by general formula (1) and a compound (B) represented bygeneral formula (2). The composition of the present embodimentpreferably has a content of the compound (A) of 95.0% by mass or more,but is not limited to this example. The composition of the presentembodiment contains 0.00002 to 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A).(R₁—COO)_(n)—R₂—(NCO)_(m)  (1)(R₁—COO)_(n)—R₂—NHC(═O)NH—R₂—(OCO—R₁)_(m)  (2)

(In general formulae (1) and (2), R₁ is an ethylenically unsaturatedgroup having 2 to 7 carbon atoms. R₂ is a (m+n)-valent hydrocarbon grouphaving 1 to 7 carbon atoms and optionally contain an ether group. R₁ andR₂ of the general formula (1) are the same as R₁ and R₂ of the generalformula (2). And, n and m are integers of 1 or 2.)

In general formulae (1) and (2), R₁ is an ethylenically unsaturatedgroup having 2 to 7 carbon atoms. The ethylenically unsaturated bond ofR₁ may be one or two or more. When the number of carbon atoms is 6 ormore, the reactivity of the ethylenically unsaturated group is lowered,so that R₁ is preferably an ethylenically unsaturated group having 2 to5 carbon atoms. The carbon number is preferably 2 to 3 or 4 to 5. Amongthe ethylenically unsaturated groups having 2 to 5 carbon atoms, R₁ ispreferably CH₂═C(CH₃)— or a vinyl group because the raw material iseasily available.

In the formulae (1) and (2), R₂ is an m+n valent hydrocarbon grouphaving 1 to 7 carbon atoms and the hydrocarbon group may be a linear orbranched chain. The carbon number of the m+n valent hydrocarbon grouprepresented by R₂ is preferably any one of 2 to 4, and more preferably2. R₂ may contain an ether group. R₂ is preferably an ethylene group, amethylene group, or —CH₂CH₂OCH₂CH₂— in view of the availability of theraw materials.

R₁ of the general formula (1) is the same as R₁ of the general formula(2) and R₂ of the general formula (1) is the same as R₂ of the generalformula (2).

In general formulae (1) and (2), n and m are integers of 1 or 2, andboth are preferably 1 in view of ease of synthesis.

As the compound (A) represented by general formula (1), for example, atleast one compound selected from the group consisting of2-methacryloyloxyethyl isocyanate, 3-methacryloyloxy-n-propylisocyanate, 2-methacryloyloxyisopropyl isocyanate,4-methacryloyloxy-n-butyl isocyanate, 2-methacryloyloxy-tert-butylisocyanate, 2-methacryloyloxybutyl-4-isocyanate,2-methacryloyloxybutyl-3-isocyanate,2-methacryloyloxybutyl-2-isocyanate,2-methacryloyloxybutyl-1-isocyanate, 5-methacryloyloxy-n-pentylisocyanate, 6-methacryloyloxy-n-hexyl isocyanate,7-methacryloyloxyn-heptylisocyanate, 2-(isocyanatoethyloxy) ethylmethacrylate, 3-methacryloyloxyphenyl isocyanate, 2-acryloyloxyethylisocyanate, and 2-acryloyloxyisocyanate, 3-acryloyloxy-n-propylisocyanate, 2-acryloyloxyisopropyl isocyanate, 4-acryloyloxy-n-butylisocyanate, 2-acryloyloxy-tert-butyl isocyanate, 2-acryloyloxybutyl-4isocyanate, 2-acryloyloxybutyl-3-isocyanate,2-acryloyloxybutyl-2-isocyanate, 2-acryloyloxybutyl-1-isocyanate,5-acryloyloxy-n-pentyl isocyanate, 6-acryloyloxy-n-hexyl isocyanate,7-acryloyloxy-n-heptyl isocyanate, 2-(isocyanatoethyloxy) ethylacrylate, 3-acryloyloxyphenyl isocyanate, 4-acryloyloxyphenylisocyanate, 1,1-bis(methacryloyloxymethyl) methyl isocyanate,1,1-bis(methacryloyloxymethyl) ethyl isocyanate,1,1-bis(acryloyloxymethyl) methyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, and 2′-pentenoyl-4-oxyphenyl isocyanate is used. Amongthese compounds, especially in view of ease of synthesis andavailability of raw materials, the compound (A) is preferably2-methacryloyloxyethyl isocyanate (examples of specific products:KarenzMOI (registered trademark)), 2-acryloyloxyethyl isocyanate(example of specific product: KarenzMOI (registered trademark)),2-(isocyanatoethyloxy)ethyl methacrylate (example of specific product:KarenzMOI-EG (registered trademark)), 2-(isocyanatoethyloxy)ethylacrylate (example of specific product: KarenzAOI-EG), or1,1-bis(methacryloyloxymethyl)ethyl isocyanate (example of specificproduct: KarenzBEI (registered trademark)). It should be noted that theproducts including Karenz in the registered trademark described hereinare available from Showa Denko K.K.

The content of the compound (A) in the composition of this embodiment ispreferably 95.0% by mass or more, more preferably 97.0% by mass or more,and more preferably 98.0% by mass to 99.9% by mass. The content may befrom 96.00% by mass to 99.99% by mass or from 97.00% by mass to 99.50%by mass, if necessary.

When the content of the compound (A) in the composition is 95.0% by massor more, it can be suitably used as a raw material for producing anunsaturated compound. When the content of the compound (A) is 99.9% bymass or less, the composition can be efficiently produced by a method ofpurification by distillation process, which is preferable. The contentof the compound (A) in the composition of the present embodiment is notlimited to the above, and can be optionally selected as necessary. Forexample, the amount of the lower limit of the content of the compound(A) may be 1.0% by mass or more, 10% by mass or more, 30% by mass ormore, 50% by mass or more, 70% by mass or more, or 80% by mass or more.

In the compound (B) represented by the general formula (2), R₁ and R₂ ofthe general formula (1) and the general formula (2) are the same. Thecompound (B) represented by the general formula (2) is presumed to be animpurity which is by-produced when the compound (A) represented by thegeneral formula (1) is produced by a production method described later.The compound (B) degrades the stability of the composition duringstorage and utilization.

In the present embodiment, with respect to 100 parts by mass of thecompound (A), 0.00002 to 2.0 parts by mass of the compound (B) arecontained in the composition. Since the content of the compound (B) withrespect to 100 parts by mass of the compound (A) in the composition is2.0 parts by mass or less, excellent stability in storage and stabilityin use can be obtained. The content of the compound (B) with respect to100 parts by mass of the compound (A) in the composition is preferably1.0 parts by mass or less, and more preferably 0.5 parts by mass orless. The stability during storage and the stability during use can befurther improved by setting the content of the compound (B) with respectto 100 parts by mass of the compound (A) in the composition within theabove-mentioned range. Further, since the content of the compound (B)with respect to 100 parts by mass of the compound (A) in the compositionis 0.00002 parts by mass or more, a yield in producing the compound (A)can be ensured, and the composition can be produced in a high yield. Thecontent of the compound (B) with respect to 100 parts by mass of thecompound (A) in the composition is preferably 0.0002 parts by mass ormore in order to further improve the yield of the compound (A).

The composition of the present invention may contain an additive inaddition to the compound (A) and the compound (B) to the extent that theeffect of the present invention is not impaired.

Examples of additives include polymerization inhibitors such ashydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol,cresol, 2,6-di-tert-butyl-4-methylphenol (BHT), phenothiazine, and thelike.

The composition of the present embodiment is preferably contained in acontainer filled with dry nitrogen gas having a dew point of −30° C. orlower in a gas phase portion. Thus, the contact of the compound (A) inthe composition after the distillation process with water is prevented,and the increase of the compound (B) in the composition is suppressed.As a result, stability during storage and stability during use areimproved.

As described above, since the composition of the present embodiment hasexcellent stability during storage and stability during use, it is notnecessary to contain a large amount of a polymerization inhibitor whichproduces a colored component.

Therefore, it is possible to prevent the unsaturated compound producedby using the composition of the present invention from being colored bythe coloring component caused by the polymerization inhibitor.

The composition of the present invention can be produced in high yield.

“Method for Producing Composition”

The method of producing the composition of the present embodiment is amethod of producing the composition contained in a container.

The method of producing the composition of the present embodimentcomprises a step of producing a mixture which contains compound (A)represented by general formula (1) and a compound (B) represented bygeneral formula (2) and which contains more than 2.0 parts by mass ofthe compound (B) with respect to 100 parts by mass of the compound (A),and purifying the mixture by a distillation process at a reflux ratio of2.0 to 4.0, a pressure of 1.0 to 10.0 kPa, and a distillationtemperature of 90 to 140° C. The content of the compound (A) of thepurified product (the composition) obtained by purification ispreferably 95.0% by mass or more as described above, but is not limitedthereto. Containing more than 2.0 parts by mass of the compound (B) withrespect to 100 parts by mass of the compound (A) means to contain 2.0parts by mass or more of the compound (B) with respect to 100 parts bymass of the compound (A).

(Step of Producing Mixture)

A method of producing a mixture which contains a compound (A) and acompound (B) and which contains more than 2.0 parts by mass of thecompound (B) with respect to 100 parts by mass of the compound (A) canbe arbitrarily selected, for example, a method of producing the compound(A) and producing the compound (B) simultaneously by using aconventionally known method of producing the compound (A) may be used.

Specifically, for example, the following methods and the like can beused. First, an unsaturated carboxylic acid aminoalkyl esterhydrochloride is synthesized by the reaction of an unsaturatedcarboxylic acid chloride with an amino alcohol hydrochloride. Next, anunsaturated carboxylic acid aminoalkyl ester hydrochloride is reactedwith carbonyl chloride. Thus, the unsaturated carboxylic acidisocyanatoalkyl ester of the compound (A) is produced. At the same time,the compound (A) is reacted with an unsaturated carboxylic acidaminoalkyl ester hydrochloride to produce a compound (B), as aby-product, which is an impurity. However, it is not limited to thismethod.

The mixture of the compound (A) and the compound (B) thus obtainedgenerally contains more than 2.0 parts by mass of the compound (B) withrespect to 100 parts by mass of the compound (A).

The upper limit of the amount of the compound (B) contained in themixture can be arbitrarily selected. For example, with respect to 100parts by mass of the compound (A), the amount of the compound (B) isgenerally 10 parts by mass or less, preferably 8 parts by mass or less,and more preferably 6 parts by mass or less. However, the presentinvention is not limited to these examples.

The content of the compound (A) contained in the mixture can bearbitrarily selected, for example, the content of the compound (A) inthe mixture is 55 to 85% by mass, may be 60 to 80% by mass, and ispreferably 65 to 75% by mass. However, it is not limited to these.

(Purifying Step)

<Distillation Process>

In the present embodiment, the mixture of the compound (A) and thecompound (B) thus obtained is purified by a distillation process at areflux ratio (reflux/distillate) of 2.0 to 4.0, a pressure of 1.0 to10.0 kPa, and a distillation temperature of 90 to 140° C. and thecompound (A) is recovered as a low-boiling component. As a result, apurified product in which the content of the compound (B) with respectto 100 parts by mass of the compound (A) is 0.00002 to 2.0 parts by massis obtained. Since compound (A) is usually a liquid, no solvent isrequired.

In the present embodiment, since the mixture is purified by thedistillation process at the reflux ratio of 2.0 to 4.0, the compound (B)can be efficiently removed. When the reflux ratio is less than 2.0,since the physical properties of the compound (A) and the compound (B)are similar, the compound (B) cannot be sufficiently removed, and thecontent of the compound (B) with respect to 100 parts by mass of thecompound (A) does not fall below 2.0 parts by mass. The reflux ratio ispreferably 2.5 or more, more preferably 3.0 or more, in order to furtherreduce the content of the compound (B). When the reflux ratio is 4.0 orless, the purifying step can be carried out efficiently in a short time,the yield of the compound (A) in the composition can be sufficientlyensured, and the composition can be produced in a high yield. The refluxratio is preferably 3.5 or less, more preferably 3.0 or less, in orderto perform the purifying step more efficiently and further improve theyield of the compound (A).

In this embodiment, the distillation temperature in the purifying stepis 90° C. to 140° C. When the distillation temperature is less than 90°C., the compound (A) and the compound (B) cannot be sufficientlyseparated, and the content of the compound (B) with respect to 100 partsby mass of the compound (A) does not become 2.0 parts by mass or less.Further, when the distillation temperature is 140° C. or lower, thecompound (A) is not lost more than necessary, the yield of the compound(A) can be ensured, and the purifying step can be efficiently performed.In order to sufficiently remove compound (B) and to improve the yield ofcompound (A), the distillation temperature is preferably from 100° C. to130° C., and more preferably from 110° C. to 120° C.

In this embodiment, the pressure at the time of distillation in thepurifying step is 1.0 to 10.0 kPa, and preferably 1.0 to 6.0 kPa. Whenthe pressure is 1.0 kPa or more, a flooding phenomenon is unlikelygenerated at a distillation temperature of 90 to 140° C., and a stabledistillation state is easily maintained. When the pressure is 10.0 kPaor less, the compound (A) and the compound (B) are easily separated at adistillation temperature of 140° C. or lower, and the loss of thecompound (A) due to increasing the distillation temperature ispreferably suppressed.

When the distillation step is performed in the purifying step, apolymerization inhibitor may be added to the mixture before heating ofthe mixture is started. By adding the polymerization inhibitor to themixture before starting the heating of the mixture, the mixture isprevented from Gelation by polymerization due to the temperature riseaccompanying the distillation.

The polymerization inhibitor added to the mixture is partially removedby the distillation process. The polymerization inhibitor remaining inthe composition after the distillation process prevents the compositionfrom Gelation during storage and transportation of the composition andcontributes to improvement of stability during storage of thecomposition. The polymerization inhibitor may optionally be added to thecomposition obtained after the distillation process.

Specific examples of the polymerization inhibitor include hydroquinone,methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol,2,6-di-tert-butyl-4-methylphenol (BHT), phenothiazine and the like.

In the purifying step, a vacuum breaking step is performed in which drynitrogen gas having a dew point of −30° C. or lower is supplied into adistillation apparatus after the distillation process and the pressurein the distillation apparatus is returned to atmospheric pressure, and afilling step is performed in which the purified product in thedistillation apparatus after the distillation process is stored in acontainer and the gas phase portion in the container is filled with drynitrogen gas having a dew point of −30° C. or lower.

In the distillation apparatus at the time of the vacuum breaking step,the condition is such that the compound (B) is easily produced in thepurified product. In the present embodiment, in the vacuum breakingstep, dry nitrogen gas having a dew point of −30° C. or lower issupplied into the distillation apparatus after the distillation processto return the pressure in the distillation apparatus to atmosphericpressure, so that contact between the compound (A) in the purifiedproduct after the distillation process and moisture can be prevented.Further, in the present embodiment, the dry nitrogen gas having a dewpoint of −30° C. or lower is filled in the gas phase portion in thecontainer in the filling step, so that contact between the compound (A)and moisture in the composition stored in the container can beprevented. Therefore, the formation or increase of the compound (B) inthe composition can be prevented by performing the vacuum breaking stepand the filling step. Therefore, the stability during storage and thestability during use are improved.

The dew point of the dry nitrogen gas supplied into the distillationapparatus in the vacuum breaking step and the dry nitrogen gas filledinto the gas phase portion in the container in the filling step is −30°C. or lower and preferably −40° C. or lower in order to suppress theformation and increase of the compound (B) in the purified product. Thedew point of the dry nitrogen gas used in the vacuum breaking step andthe filling step is preferably −70° C. or higher because it isindustrially readily available. It has been confirmed that even when thedew point of dry nitrogen gas is −70° C. or higher and less than −60°C., the same effect as that of dry nitrogen gas having a dew point of−60° C. or higher and −30° C. or lower can be obtained.

In the present embodiment, in order to more effectively prevent theincrease of the compound (B) in the purified product, it is preferablethat the purified product does not come into contact with a gas otherthan dry nitrogen gas having a dew point of −30° C. or lower in the stepof feeding the purified product in the distillation apparatus after thedistillation process into a container.

[Method for Producing Unsaturated Compound]

The method of producing an unsaturated compound according to the presentembodiment includes a step of mixing the composition with a compoundhaving active hydrogen and reacting the compound (A) contained in thecomposition with the compound having active hydrogen to obtain areaction product (unsaturated compound).

In the present embodiment, the compound (A) contained in the compositionused as the material of the unsaturated compound (reaction product) canbe appropriately selected according to the structure of the unsaturatedcompound to be produced.

The active hydrogen in the compound having the active hydrogen is ahydrogen atom bonded to a nitrogen atom, an oxygen atom, a sulfur atomor the like, and exhibits high reactivity as compared with a hydrogenatom bonded to a carbon atom. The compound having active hydrogen is notparticularly limited, and can be appropriately selected according to thestructure of the unsaturated compound.

For example, when a compound having an active hydrogen-containing group,such as a hydroxyl group, a mercapto group, an amino group (includingcyclic amines, amides and imides), and a carboxy group, is used as theactive hydrogen-containing compound, the following reaction product(unsaturated compound) is obtained by the following reaction.

When a compound (A) contained in the composition is reacted with acompound having a hydroxyl group, the isocyanate group of the compound(A) reacts with the hydroxyl group to form an unsaturated urethanecompound. In this embodiment, the unsaturated urethane compound means acompound containing an ethylenically unsaturated bond and a urethanebond in the molecule.

When a compound (A) contained in the composition is reacted with acompound having a mercapto group, the isocyanato group of the compound(A) is reacted with the mercapto group to form an unsaturatedthiourethane compound. In this embodiment, the unsaturated thiourethanecompound means a compound containing an ethylenically unsaturated bondand a thiourethane bond in the molecule.

When a compound (A) contained in the composition is reacted with acompound having an amino group, the isocyanate group of the compound (A)is reacted with the amino group to form an unsaturated urea compound. Inthis embodiment, the unsaturated urea compound means a compoundcontaining an ethylenically unsaturated bond and a urea bond in themolecule.

When a compound (A) contained in the composition is reacted with acompound having a carboxy group, the isocyanato group of the compound(A) is reacted with the carboxy group to form an unsaturated amidecompound. In this embodiment, the unsaturated amide compound means acompound containing an ethylenically unsaturated bond and an amide bondin the molecule.

The compound having a hydroxyl group can be arbitrarily selected,examples thereof include an aliphatic alcohol compound such as ethanol,n- or iso-propanol, butanol or its isomer, pentanol, hexanol, octanol,decanol, or the like; phenolic compounds such as phenol, cresol,p-nonylphenol, methyl salicylate; aliphatic polyols such as ethyleneglycol, diethylene glycol, propylene glycol, tetramethylenediol,neopentyl glycol, 1,6-hexanediol, glycerol, trimethylolethane,trimethylolpropane, butanetriol, pentaerythritol, dipentaerythritol,tripentaerythritol, sorbitol, hexanetriol, triglycerol, polyethyleneglycol, polypropylene glycol, ethylene oxide and propylene oxidecopolymers, tris(2-hydroxyethyl) isocyanurate, cyclohexanediol,cyclohexanedimethanol, hydroxypropylhexanol, tricyclo [5, 2, 3,0^(2, 6)] decanedimethanol, dicyclohexanediol, or the like; aromaticpolyols such as dihydroxynaphthalene, dihydroxybenzene, bisphenol-A,bisphenol-F, pyrogallol, xylene glycol, bisphenol-A (2-hydroxyethylether); halogenated polyols such as dibromoneopentyl glycol; hydroxylgroup-containing epoxy resin; phenoxy resin; polymeric polyols such aspolyvinyl alcohol and (co) polymers of hydroxyethyl (meta) acrylate;terminal hydroxyl-containing reaction product obtained by reacting theabove-mentioned polyol with an organic acid such as phthalic acid,pyromellitic acid, trimellitic acid, adipic acid, dimer acid or thelike; addition reaction product of the above-mentioned polyols andalkylene oxide (ethylene oxide, propylene oxide, and the like); glucosederivatives such as hydroxyethyl cellulose and nitrocellulose;heterocycle-containing alcohols such as the carboxylic acid (formicacid, acetic acid, benzoic acid, or the like) orthoester ofpentaerythritol; groups with both hydrogen atom and mercapto group, suchas 2-mercaptoethanol; oxime-based compounds such as dimethyl ketoneoxime, diethyl ketone oxime, methyl ethyl ketone oxime (MEK oxime) orthe like; and the like.

Among the compounds having a hydroxyl group, polyol is preferable, andaliphatic polyol is more preferable.

The compound having the mercapto group can be optionally selected, andexamples thereof include monothiols such as 1-butanethiol,1-pentanethiol, 1-octanethiol, 1-dodecanethiol, n-octadecanethiol,α-toluenethiol, 2-benzimidazolethiol, 2-thiazoline-2-thiol,2-methyl-2-propunchol, o-aminothiophenol, or the like; hexanedithiol,decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycolbisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanetrithioglycolate, trimethylolpropane tristhiopropionate,trimethylolpropane tristhiopropionate (3-mercaptobutylate),pentaerythritol tetrakis (2-mercaptopropionate), trimercaptopropionatetris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,2,4,6-trimercapto-s-triazine, 2-(N, N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate),tris(3-mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis3-mercaptopropionate, aliphatic polythiols, such as dipentaerythritoltetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane(examples of specific products: “KarenzMT (registered trademark) PE1”),1,3,5-tris(3-mercaptobutylate)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione(examples of specific products: “KarenzMT(registered trademark) NR1”),pentaerythritol tetrakis (3-mercaptobutylate) (examples of specificproducts: “KarenzMT (registered trademark) PE1”); and the like.

Among the compounds having a mercapto group, polythiol is preferable,and aliphatic polythiol is more preferable.

The compound having an amino group can be arbitrarily selected, butexamples thereof include a monoamine such as butylamine, hexylamine oraniline; aliphatic polyamines such as diethylenetriamine,triethylenetetramine, 1,3- or 1,4-bisaminomethylcyclohexane,isophoronediamine, hexamethylenediamine, bis(4-aminocyclohexyl) methaneor the like; aromatic polyamines such as m- or p-xylylenediamine,bis(4-aminophenyl) methane, 2,4- or 2,6-tolylenediamine or the like;glucosamines such as chitosan or the like; silicone compounds such asbis(3-aminopropyl) polydimethylsiloxane and bis(3-aminopropyl)polydiphenylsiloxane; heterocycle-containing compounds such asimidazole, E-caprolactam, phthalimide or the like; amides; imides;2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (examplesof specific products: “KarenzMOI-BP (registered trademark)”);2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate;3,5-dimethylpyrazole; and the like.

Among the compounds having an amino group, polyamines are preferable,and aliphatic polyamines are more preferable.

The compound having a carboxy group can be arbitrarily selected, but amonocarboxylic acid such as acetic acid, propionic acid, decanoic acidor the like; aliphatic and aromatic polycarboxylic acids such assuccinic acid, adipic acid, phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, pyromellitic acid or the like;polymeric polycarboxylic acids such as polyamic acids, (co) polymers ofacrylic acids or the like can be used.

Among the compounds having a carboxy group, polycarboxylic acids arepreferable, and aliphatic and aromatic polycarboxylic acids are morepreferable.

Further, as the compound having the active hydrogen, a halogensubstitution such as a fluorine substitution or a chlorine substitutionof the compound having the active hydrogen may be used. These may beused alone or in combination of two or more.

The active hydrogen-containing compound is preferably a polyol, apolythiol, a polyamine or a polycarboxylic acid in view of versatility,and is particularly preferably a polyol.

In the reaction of the compound (A) contained in the composition of thepresent embodiment with the compound having active hydrogen, the ratioof the compound (A) to the compound having active hydrogen is set inconsideration of the ratio of isocyanate groups/active hydrogen.

The isocyanato group/active hydrogen ratio may be the same as thatconventionally applied in the reaction of compound (A) with a compoundhaving active hydrogen. The ratio of isocyanato group to active hydrogenvaries depending on the kind of compound having active hydrogen.

The compound (A) contained in the composition of the present embodimentand the compound having active hydrogen may be reacted in the presenceof a reaction catalyst. The reaction rate can be controlled by theaddition amount of the reaction catalyst.

As the reaction catalyst, a known reaction catalyst can be used.Specific examples of reaction catalysts include dibutyltin dilaurate,copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine,1,4-diazabicyclo[2.2.2]octane, zirconium acetylacetonate, titaniumdiisopropoxybis(ethyl acetoacetate), mixtures of bismuthtris(2-ethylhexanoate) and 2-ethylhexanoic acid, and the like. Thesereaction catalysts may be used singly or in combination of two or more.

When the compound (A) contained in the composition of the presentembodiment is reacted with a compound having active hydrogen, thereaction temperature is preferably −10 to 100° C., and more preferably 0to 80° C.

When the compound (A) contained in the composition of the presentembodiment is reacted with a compound having active hydrogen, apolymerization inhibitor may be added if necessary. As thepolymerization inhibitor, a generally used one can be used, for example,a phenolic compound, a hydroquinone compound or the like can be used.Specific examples of polymerization inhibitors include hydroquinone,methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol,2,6-di-tert-butyl-4-methylphenol (BHT), and the like.

In addition, various substances such as known light stabilizers,ultraviolet absorbers, antioxidants, dye fillers, reactive diluents andthe like may be added according to the purpose of the reaction.

The unsaturated compound (reaction product) is preferably at least oneselected from the group consisting of unsaturated urethane compounds,unsaturated thiourethane compounds, unsaturated urea compounds andunsaturated amide compounds, and more preferably at least one selectedfrom the group consisting of 2-butanoneoxime-O-(carbamoylethyl-2-methacrylate),2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, 2-butanoneoxime-O-(carbamoylethyl-2-acrylate) and2-[(3,5-dimethylpyrazolyl)carbonylamino] ethyl acrylate.

The unsaturated compound thus obtained is preferably used as a materialin various fields such as coating materials, adhesives, photoresists,contact lenses, solid electrolytes, solidification of bioactivesubstances or the like.

The composition of the present embodiment is a composition whichcontains a compound (A) represented by general formula (1) and acompound (B) represented by general formula (2) and which contains0.00002 to 2.0 parts by mass of the compound (B) with respect to 100parts by mass of the compound (A). Therefore, it is excellent instability during storage and stability during use. Further, it is notnecessary to contain a large amount of the polymerization inhibitorwhich forms the colored component. Therefore, it is possible to preventthe unsaturated compound produced by using the composition of thepresent embodiment from being colored by the coloring component causedby the polymerization inhibitor.

Further, since the composition of the present embodiment contains0.00002 parts by mass or more of the compound (B) with respect to 100parts by mass of the compound (A), the composition can be produced in ahigh yield.

In the method of producing the composition of the present embodiment, amixture, which contains more than 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A), is purified by adistillation process at a reflux ratio of 2.0 to 4.0, a pressure of 1.0to 10.0 kPa, and a distillation temperature of 90 to 140° C. to obtain apurified product containing 0.00002 to 2.0 parts by mass of the compound(B) with respect to 100 parts by mass of the compound (A). Therefore,according to the method of producing the composition of the presentembodiment, the composition of the present embodiment can be produced ina high yield in which the compound (B) that affects the stability duringstorage and affects the stability during use is sufficiently removedfrom the mixture.

Further, in the method of producing the composition of the presentembodiment, in the purifying step, a vacuum breaking step and a fillingstep are carried out, and in the vacuum breaking step, dry nitrogen gashaving a dew point of −30° C. or lower is supplied into the distillationapparatus after the distillation process and the pressure in thedistillation apparatus is returned to atmospheric pressure; and in thefilling step, the purified product in the distillation apparatus afterthe distillation process is stored in a container and the gas phaseportion in the container is filled with dry nitrogen gas having a dewpoint of −30° C. or lower. Therefore, the compound (A) in the purifiedproduct after distillation process is unlikely brought into contact withwater, and the compound (B) is unlikely increased in the purifiedproduct. Therefore, according to the method of producing the compositionof the present embodiment, a composition having good stability duringstorage and stability during use can be obtained.

The method of producing the unsaturated compound of the presentembodiment includes a step of mixing the composition of the presentinvention with a compound having active hydrogen and reacting thecompound (A) contained in the composition with the compound havingactive hydrogen to obtain a reaction product. In the method of producingthe unsaturated compound according to the present embodiment, thecomposition used as the material contains 0.00002 to 2.0 parts by massof the compound (B) with respect to 100 parts by mass of the compound(A). Therefore, rapid increase in viscosity or gelation of the reactionproduct is unlikely to occur during production, and excellentproductivity is obtained.

EXAMPLES

Hereinafter, this embodiment will be described in detail with referenceto Examples and Comparative Examples. It should be noted that thefollowing embodiments are intended to facilitate understanding of thecontents of the present embodiment, and the present embodiment is notlimited only to these embodiments.

Mixture 1 and Mixture 2 were prepared by the following methods.

<Mixture 1> (Synthesis of MOI)

In a 500 ml four-necked flask equipped with a stirrer, condenser,thermometer and inner tube, 250 ml of toluene and 25 g (0.41 mol) of2-aminoethanol were added, heated to 90° C. and supplied with about 20 gof hydrogen chloride gas. Then, 44 g (0.42 mol) of methacrylic acidchloride was added dropwise, and the mixture was heated at 90° C. for 1hour. Thereafter, 80 g (0.81 mol) of phosgene was supplied. 0.4 g ofphenothiazine and 0.4 g of 2,6-bis-tert-butylhydroxytoluene were thenadded, and dissolved phosgene and toluene were removed.

By the above process, Mixture 1 containing the main product (thecompound (A)) of 2-methacryloyloxyethyl isocyanate (MOI) 45 g (0.29 mol)(71% yield) and the by-product (the compound (B)) of N,N′-bis(2-methacryloyloxyethyl) urea (56375 ppm by mass) was obtained.

<Mixture 2> (Synthesis of AOI)

In a 500 mL four-necked flask equipped with a stirrer, condenser,thermometer and inner tube, 250 mL of toluene and 25 g (0.41 mol) of2-aminoethanol were added, heated to 90° C. and supplied with about 20 gof hydrogen chloride gas. Then 56 g (0.44 mol) of 3-chloropropionic acidchloride was added dropwise over 90 minutes and heated at 90° C. for 1hour. Thereafter, 80 g (0.81 mol) of phosgene was supplied. Dissolvedphosgene was then removed by nitrogen gas bubbling. Subsequently, 0.4 gof phenothiazine and 0.4 g of 2,6-bis-t-butylhydroxytoluene were added,and 50 g of triethylamine (0.49 mol) was supplied, and the mixture washeated and stirred at 50° C. for 6 hours. Thereafter, the mixture wascooled to room temperature, the formed hydrochloride salt was filtered,and toluene was distilled off.

By the above process, Mixture 2 containing the main product (thecompound (A)) of 2-acryloyloxyethyl isocyanate (AOI) 55 g (0.35 mol)(87% yield) and the by-product (the compound (B)) of N,N′-bis(2-Acryloyloxyethyl) urea (48657 ppm by mass) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 8> (MOI)

50 g of Mixture 1 was distilled under the conditions shown in Tables 1and 2 (reflux ratio (reflux/distillate), distillation temperature,distillation pressure). The liquid compositions of Examples 1 to 6 andComparative Examples 1 to 8 contained in a container were obtained bycarrying out a vacuum breaking step in which the gas shown in Tables 1and 2 was supplied into the distillation apparatus after thedistillation process to return the pressure in the distillationapparatus to atmospheric pressure, and a filling step in which thepurified product in the distillation apparatus after the distillationprocess was contained in a transparent glass container and the gas phaseportion in the container was filled with the gas shown in Tables 1 and2.

<Examples 7 to 12 and Comparative Examples 9 to 16> (AOI)

50 g of mixture 2 was distilled under the conditions shown in Tables 3and 4 (reflux ratio (reflux/distillate), distillation temperature,distillation pressure). Thereafter, in the same manner as describedabove, a vacuum breaking step of supplying the gas shown in Tables 3 and4 into the distillation apparatus after the distillation process andreturning the pressure in the distillation apparatus to the atmosphericpressure was carried out, and the filling step of storing the purifiedproduct in the distillation apparatus after the distillation process ina transparent glass container and filling the gas phase portion in thecontainer with the gas shown in Tables 3 and 4 was carried out to obtainthe liquid compositions of Examples 7 to 12 and Comparative Examples 9to 16 stored in the container.

TABLE 1 Example 1 2 3 Distillation temperature(° C.) 110 115 90Distillation pressure (kPa) 2.0 2.5 1.0 Reflux ratio 3.5 3.0 3.5 Gassupplied in the vacuum Dried nitrogen gas Dried nitrogen gas Driednitrogen gas breaking step (Dew point: −60° C.) (Dew point: −30° C.)(Dew point: −40° C.) Gas filled in the filling step Dried nitrogen gasDried nitrogen gas Dried nitrogen gas (Dew point: −50° C.) (Dew point:−50° C.) (Dew point: −30° C.) Compound A content 98.0 98.5 98.7 (% bymass) Compound B Content 154 213 759 (×10⁻⁴ parts by mass) Yield (%) 8587 90 Viscosity (mPa · sec) 1.5 1.7 1.6 Appearance No change No changeNo change Example 4 5 6 Distillation temperature(° C.) 100 135 130Distillation pressure (kPa) 1.5 6.0 6.0 Reflux ratio 2.5 2.0 4.0 Gassupplied in the vacuum Dried nitrogen gas Dried nitrogen gas Driednitrogen gas breaking step (Dew point: −35° C.) (Dew point: −40° C.)(Dew point: −30° C.) Gas filled in the filling step Dried nitrogen gasDried nitrogen gas Dried nitrogen gas (Dew point: −50° C.) (Dew point:−50° C.) (Dew point: −40° C.) Compound A content 98.2 99.2 99.4 (% bymass) Compound B Content 489 356 623 (×10⁻⁴ parts by mass) Yield (%) 8884 78 Viscosity (mPa · sec) 1.7 1.7 1.6 Appearance No change No changeNo change

TABLE 2 Comparative Example 1 2 3 4 Distillation temperature(° C.) 90110 135 110 Distillation pressure (kPa) 1.0 2.0 6.5 2.0 Reflux ratio 1.00.2 1.5 0.5 Gas supplied in the vacuum Dried nitrogen gas Dried nitrogengas Dried nitrogen gas Dried nitrogen gas breaking step (Dew point: −40°C.) (Dew point: −30° C.) (Dew point: −20° C.) (Dew point: −30° C.) Gasfilled in the filling step Dried nitrogen gas Dried nitrogen gas Driednitrogen gas Dried nitrogen gas (Dew point: −30° C.) (Dew point: −50°C.) (Dew point: −40° C.) (Dew point: −20° C.) Compound A content 97.597.0 97.8 96.3 (% by mass) Compound B Content 25317 23007 24006 28648(×10⁻⁴ parts by mass) Yield (%) 93 90 85 88 Viscosity (mPa · sec) Notmeasurable Not measurable Not measurable Not measurable AppearanceSyrup-like Solid Syrup-like Solid Comparative Example 5 6 7 8Distillation temperature(° C.) 90 100 135 130 Distillation pressure(kPa) 1.0 1.5 6.0 6.0 Reflux ratio 3.5 2.5 2.0 4.5 Gas supplied in thevacuum Air Dried nitrogen gas Dried nitrogen gas Air breaking step (Dewpoint: −40° C.) (Dew point: −50° C.) Gas filled in the filling stepDried nitrogen gas Air Air Dried nitrogen gas (Dew point: −50° C.) (Dewpoint: −30° C.) Compound A content 98.2 97.7 98.7 98.9 (% by mass)Compound B Content 32546 58975 35687 66458 (×10⁻⁴ parts by mass) Yield(%) 90 88 84 78 Viscosity (mPa · sec) Not measurable Not measurable Notmeasurable Not measurable Appearance Syrup-like Solid Syrup-like Solid

TABLE 3 Example 7 8 9 Distillation temperature(° C.) 90 120 130Distillation pressure (kPa) 1.5 3.5 6.5 Reflux ratio 3.5 2.0 3.5 Gassupplied in the vacuum Dried nitrogen gas Dried nitrogen gas Driednitrogen gas breaking step (Dew point: −60° C.) (Dew point: −60° C.)(Dew point: −40° C.) Gas filled in the filling step Dried nitrogen gasDried nitrogen gas Dried nitrogen gas (Dew point: −40° C.) (Dew point:−30° C.) (Dew point: −40° C.) Compound A content 98.6 98.5 99.4 (% bymass) Compound B Content 358 487 523 (×10⁻⁴ parts by mass) Yield (%) 8882 80 Viscosity(mPa · sec) 1.6 1.8 1.6 Appearance No change No change Nochange Example 10 11 12 Distillation temperature(° C.) 110 115 125Distillation pressure (kPa) 2.5 3.0 4.5 Reflux ratio 2.5 2.0 4.0 Gassupplied in the vacuum Dried nitrogen gas Dried nitrogen gas Driednitrogen gas breaking step (Dew point: −30° C.) (Dew point: −50° C) (Dewpoint: −30° C.) Gas filled in the filling step Dried nitrogen gas Driednitrogen gas Dried nitrogen gas (Dew point: −40° C.) (Dew point: −60°C.) (Dew point: −40° C.) Compound A content 98.2 99.2 99.6 (% by mass)Compound B Content 654 338 597 (×10⁻⁴ parts by mass) Yield (%) 86 84 72Viscosity(mPa · sec) 1.7 1.7 1.6 Appearance No change No change Nochange

TABLE 4 Comparative Example 9 10 11 12 Distillation temperature(° C.) 90110 130 110 Distillation pressure (kPa) 1.5 2.5 6.5 2.5 Reflux ratio 10.2 1.5 0.5 Gas supplied in the vacuum Dried nitrogen gas Dried nitrogengas Dried nitrogen gas Dried nitrogen gas breaking step (Dew point: −50°C.) (Dew point: −60° C.) (Dew point: −30° C.) (Dew point: −40° C.) Gasfilled in the filling step Dried nitrogen gas Dried nitrogen gas Driednitrogen gas Dried nitrogen gas (Dew point: −60° C.) (Dew point: −40°C.) (Dew point: −50° C) (Dew point: −50° C.) Compound A content 97.597.0 97.8 96.3 (% by mass) Compound B Content 26578 22897 28674 33265(×10⁻⁴ parts by mass) Yield (%) 91 90 81 88 Viscosity (mPa · sec) Notmeasurable Not measurable Not measurable Not measurable AppearanceSyrup-like Solid Syrup-like Solid Comparative Example 13 14 15 16Distillation temperature(° C.) 130 110 115 125 Distillation pressure(kPa) 6.5 2.5 3.0 4.5 Reflux ratio 3.5 2.5 2.0 4.5 Gas supplied in thevacuum Air Dried nitrogen gas Dried nitrogen gas Air breaking step (Dewpoint: −40° C.) (Dew point: −50° C.) Gas filled in the filling stepDried nitrogen gas Air Air Dried nitrogen gas (Dew point: −60° C.) (Dewpoint: −30° C.) Compound A content 99.4 98.2 99.2 99.6 (% by mass)Compound B Content 35687 43652 37885 56782 (×10⁻⁴ parts by mass) Yield(%) 80 86 84 72 Viscosity (mPa · sec) Not measurable Not measurable Notmeasurable Not measurable Appearance Syrup-like Solid Syrup-like Solid

Next, regarding the compositions of Examples 1 to 12 and ComparativeExamples 1 to 16, the compound (A) and the compound (B) in each thecomposition were determined quantitatively by the following method, andthe content (% by mass) of the compound (A) and the content (×10⁻⁴ partsby mass) of the compound (B) with respect to100 parts by mass of thecompound (A) in each the composition were determined. The results areshown in Tables 1 to 4.

<Quantification of Compound (A) and Compound (B)>

The composition was subjected to gas chromatography (GC) analysis by aninternal standard method under the following conditions.

Column: DB-1, Inlet Temperature: 300° C., Detection Temperature: 300° C.

Column temperature: 50° C. to 300° C. at 10° C./min

Column flow rate: 1.4 ml/min

Split ratio: 1/50

Detector: FID

The yields (distillation yield) of the compositions (crude products) ofExamples 1 to 12 and Comparative Examples 1 to 16 were determined by thefollowing formula. The results are shown in Tables 1 to 4.

Yield=(the composition Mass/Theoretical Yield)×100(%)

“Appearance Evaluation”

In Examples 1 to 12 and Comparative Examples 1 to 16, 100 g of theliquid compositions immediately after the distillation process werestored in a transparent glass container in a sealed state at 25° C. for30 days under a nitrogen gas atmosphere, and the appearance afterstorage was evaluated by the following method.

The transparent glass container containing the composition was tiltedseveral times at an angle of about 45 degrees and evaluated visuallyusing the following criteria. The results are shown in Tables 1 to 4.

“Criteria”

No change: flowing in less than 30 seconds after tilting the glasscontainer

Syrup-like: flowing down in 30 seconds or more and less than 180 secondsafter tilting a glass container

Solid: not flowing in more than 180 seconds after tilting the glasscontainer

“Method of Measuring Viscosity”

The viscosities of the compositions of Examples 1 to 12 and ComparativeExamples 1 to 16 stored at 25° C. for 30 days in a sealed state weredetermined in accordance with JIS-Z 8803: 2011 by the following method.The results are shown in Tables 1 to 4.

The kinematic viscosity (cm³/sec) of each composition at 25° C. wasmeasured using an Uberode viscometer. In Examples 1 to 6 and ComparativeExamples 1 to 8, the measured kinematic viscosity was multiplied by thedensity of the following KarenzMOI (registered trademark) (manufacturedby Showa Denko) to calculate the viscosity (mPa·sec). In Examples 7 to12 and Comparative Examples 9 to 16, the viscosity was calculated bymultiplying the measured value of the kinematic viscosity by the densityof the KarenzAOI (registered trademark) (manufactured by Showa Denko)shown below (mPa·sec).

(Density of the KarenzMOI (registered trademark)) 1.096 g/cm³ (25° C.)

(Density of KarenzAOI (registered trademark)) 1.133 g/cm³ (25° C.)

As shown in Tables 1 to 4, the compositions of Examples 1 to 12, whichcontain 0.00002 to 2.0 parts by mass of Compound (B) with respect to 100parts by mass of Compound (A), had a sufficiently low viscosity afterstorage at 25° C. for 30 days, and the appearance evaluation were “Nochange”.

On the other hand, in the compositions of Comparative Examples 1 to 16,which contain more than 2.0 parts by mass of the compound (B) withrespect to 100 parts by mass of Compound (A), the viscosity which becametoo high by storing at 25° C. for 30 days, and the viscosity could notbe measured. In the compositions of Comparative Examples 1 to 16, theappearance evaluations were “syrup-like” or “solid”.

(Unsaturated Compound)

<Example 13> (Reaction Product of (Poly)ol with MOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 165 g of polyethylene glycol (number-average molecularweight 660) and 77.5 g of the composition of Example 1 (The compound (A)is MOI.) were charged and reacted at 80° C. for 5 hours to synthesize anunsaturated urethane compound 1.

<Comparative Example 17> (Reaction Product of (Poly)ol with MOI)

An unsaturated urethane compound 2 was synthesized in the same manner asin Example 13 except that the composition of Comparative Example 1 (Thecompound (A) is MOI.) was used in place of the composition of Example 1.

<Comparative Example 18> (Reaction Product of (Poly)ol with MOI)

An unsaturated urethane compound 3 was synthesized in the same manner asin Example 13 except that the composition of Comparative Example 7 (Thecompound (A) is MOI.) was used in place of the composition of Example 1.

<Example 14> (Reaction Product of (Poly)ol with AOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 165 g of polyethylene glycol (number-average molecularweight 660) and 70.5 g of the composition of Example 9 (The compound (A)is AOI.) were charged and reacted at 80° C. for 5 hours to synthesize anunsaturated urethane compound 4.

<Comparative Example 19> (Reaction Product of (Poly)ol with AOI)

An unsaturated urethane compound 5 was synthesized in the same manner asin Example 14 except that the composition of Comparative Example 12 (Thecompound (A) is AOI.) was used in place of the composition of Example 9.

<Comparative Example 20> (Reaction Product of (Poly)ol with AOI)

An unsaturated urethane compound 6 was synthesized in the same manner asin Example 14 except that the composition of Comparative Example 16 (Thecompound (A) is AOI.) was used in place of the composition of Example 9.

Viscosities of the reaction liquids containing the unsaturated urethanecompounds 1 to 6, obtained in Examples 13 and 14 and ComparativeExamples 17 to 20, were measured in accordance with JIS-Z 8803: 2011 at25° C. using a tuning fork type vibrating viscometer (SV type viscometermanufactured by A & D Co., Ltd. (SV −10 Type)). The results are shown inTables 5 and 6.

TABLE 5 Unsaturated Compound B Urethane Content in Composition CompoundComposition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example 13 1Example 1 154 0.16 Comparative 2 Comparative 25317 gelation Example 17Example 1 Comparative 3 Comparative 35687 gelation Example 18 Example 7

TABLE 6 Unsaturated Compound B Urethane Content in Composition CompoundComposition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example 14 4Example 9 523 0.16 Comparative 5 Comparative 33265 Gelation Example 19Example 12 Comparative 6 Comparative 56782 Gelation Example 20 Example16

As shown in Table 5, in Example 13 in which the unsaturated urethanecompounds were prepared by using the composition containing 0.00002 to2.0 parts by mass of the compound (B) with respect to 100 parts by massof the compound (A), the unsaturated urethane compound 1 having anappropriate viscosity was obtained, and the unsaturated urethanecompound could be produced without problem.

On the other hand, in Comparative Examples 17 and 18 in which theunsaturated urethane compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), the unsaturated urethane compounds 2and 3 were gelatinized during the preparation of the unsaturatedurethane compounds 2 and 3, although there was no problem in handling inthe raw material stage.

As shown in Table 6, in Example 14 in which the unsaturated urethanecompounds were prepared by using a composition containing 0.00002 to 2.0parts by mass of Compound (B) with respect to 100 parts by mass ofCompound (A), the unsaturated urethane compound 4 having an appropriateviscosity was obtained, and the unsaturated urethane compound could beproduced without any problem.

On the other hand, in Comparative Examples 19 and 20 in which theunsaturated urethane compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), the viscosity of the unsaturatedurethane compounds 5 and 6 was high, and a part of them gelled duringthe preparation.

<Example 15> (Reaction Product of (Poly)amine with MOI)

A 500 ml four-necked flask equipped with a stirrer, reflux condenser andthermometer was charged with 66.4 g of(2-[(3,5-Dimethylpyrazolyl)carbonylamino]ethyl methacrylate)(KarenzMOI-BP (registered trademark) manufactured by Showa Denko) and77.4 g of 3,5-dimethylpyrazole, and 122.6 g of the composition ofExample 2 (The compound (A) is MOL) was supplied while the temperaturewas maintained at 35° C., and then reacted for 2 hours to synthesizeunsaturated urea compound 1.

<Comparative Example 21> (Reaction Product of (Poly)amine with MOI)

The unsaturated urea compound 2 was synthesized in the same manner as inExample 15 except that the composition of Comparative Example 2 (Thecompound (A) is MOI.) was used in place of the composition of Example 2.

<Comparative Example 22> (Reaction Product of (Poly)amine with MOI)

The unsaturated urea compound 3 was synthesized in the same manner as inExample 15 except that the composition of Comparative Example 5 (Thecompound (A) is MOI.) was used in place of the composition of Example 2.

<Example 16> (Reaction Product of (Poly)amine with AOI)

In a 1000 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 115.9 g of 3,5-dimethylpyrazole and 155.0 g of2-acetoxy-1-methoxypropane were charged, 174.0 g of the composition ofExample 8 (The compound (A) is AOI.) was fed while maintaining thetemperature at 15° C., and then reacted for 30 minutes. Subsequently,320.0 g of n-hexane was added and cooled to 0° C. to crystallize anunsaturated urea compound 4. The obtained crystals were recovered byfiltration, washed with n-hexane, and dried under reduced pressure toisolate the unsaturated urea compound 4.

<Comparative Example 23> (Reaction Product of (Poly)amine with AOI.)

An unsaturated urea compound 5 was synthesized in the same manner as inExample 16 except that the composition of Comparative Example 10 (Thecompound (A) is AOI.) was used in place of the composition of Example 8.

<Comparative Example 24> (Reaction Product of (Poly)amine with AOI)

An unsaturated urea compound 6 was synthesized in the same manner as inExample 16 except that the composition of Comparative Example 15 (Thecompound (A) is AOI.) was used in place of the composition of Example 8.

Viscosities of the reaction liquids containing the unsaturated ureacompounds 1 to 6 obtained in Examples 15 and 16 and Comparative Examples21 to 24 were measured in accordance with JIS-Z 8803: 2011 at 25° C.using a tuning fork type vibration type viscometer (SV type viscometermanufactured by A & D Co., Ltd. (SV −10 Type)). The results are shown inTables 7 and 8.

TABLE 7 Unsaturated Compound B Urea Content in Composition CompoundComposition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example 15 1Example 2 213 0.18 Comparative 2 Comparative 23007 Gelation Example 21Example 2 Comparative 3 Comparative 32546 Gelation Example 22 Example 5

TABLE 8 Unsaturated Compound B Urea Content in Composition CompoundComposition (×10⁻⁴) Weight Part Viscosity (mPa · sec) Example 16 4Example 8 487 0.22 Comparative 5 Comparative 22897 Gelation Example 23Example 10 Comparative 6 Comparative 37885 Gelation Example 24 Example15

As shown in Table 7, in Example 15 in which unsaturated urea compoundswere prepared by using the composition containing 0.00002 to 2.0 partsby mass of Compound (B) with respect to 100 parts by mass of Compound(A), the unsaturated urea compound 1 having an appropriate viscosity wasobtained, and the unsaturated urea compound was successfully prepared.

On the other hand, in Comparative Examples 21 and 22 in whichunsaturated urea compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), the unsaturated urea compounds 2 and3 were gelled during the preparation, although there was no problem inhandling at the stage of raw material.

As shown in Table 8, in Example 16 in which unsaturated urea compoundswere prepared by using a composition containing 0.00002 to 2.0 parts bymass of Compound (B) with respect to 100 parts by mass of Compound (A),the unsaturated urea compound 4 having a proper viscosity was obtained,and the unsaturated urea compound was successfully prepared.

On the other hand, in Comparative Examples 23 and 24 in whichunsaturated urea compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), the unsaturated urea compounds 5 and6 were gelled during the preparation, although there was no problem inhandling at the stage of raw material.

<Example 17> (Reaction Product of (Poly)carboxylic Acid with MOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 177.3 g of decanoic acid, 156.5 g of the composition ofExample 3 (The compound (A) is MOI.) and 0.8 g of dibutyltin dilauratewere charged and reacted at 80° C. for 12 hours to synthesize anunsaturated amide compound 1.

<Comparative Example 25> (Reaction Product of (Poly)carboxylic Acid withMOI)

An unsaturated amide compound 2 was synthesized in the same manner as inExample 17 except that the composition of Comparative Example 3 (Thecompound (A) is MOI.) was used in place of the composition of Example 3.

<Comparative Example 26> (Reaction Product of (Poly)carboxylic Acid withMOI)

The unsaturated amide compound 3 was synthesized in the same manner asin Example 17 except that the composition of Comparative Example 8 (Thecompound (A) is MOI.) was used in place of the composition of Example 3.

<Example 18> (Reaction Product of (Poly)carboxylic Acid with AOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 177.3 g of decanoic acid, 142.4 g of the composition ofExample 7 (The compound (A) is AOI.) and 0.8 g of dibutyltin dilauratewere charged and reacted at 80° C. for 12 hours to synthesize anunsaturated amide compound 4.

<Comparative Example 27> (Reaction Product of (Poly)carboxylic Acid withAOI)

An unsaturated amide compound 5 was synthesized in the same manner as inExample 18 except that the composition of Comparative Example 11 (Thecompound (A) is AOI.) was used in place of the composition of Example 7.

<Comparative Example 28> (Reaction Product of (Poly)carboxylic Acid withAOI)

An unsaturated amide compound 6 was synthesized in the same manner as inExample 18 except that the composition of Comparative Example 14 (Thecompound (A) is AOI.) was used in place of the composition of Example 7.

Viscosities of the reaction liquids containing the unsaturated amidecompounds 1 to 6 obtained in Examples 17 and 18 and Comparative Examples25 to 28 were measured in accordance with JI-Z 8803: 2011 at 25° C.using a tuning fork type vibrating viscometer (SV type viscometermanufactured by A & D Co., Ltd. (SV-10 Type)).

TABLE 9 Unsaturated Compound B Amide Content in Composition CompoundComposition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example 17 1Example 3 759 0.77 Comparative 2 Comparative 24006 Gelation Example 25Example 3 Comparative 3 Comparative 66458 Gelation Example 26 Example 8

TABLE 10 Unsaturated Compound B Amide Content in Composition CompoundComposition (×10⁻⁴ parts by mass) Viscosity(mPa · sec) Example 18 4Example 7 358 0.22 Comparative 5 Comparative 28674 Gelation Example 27Example 11 Comparative 6 Comparative 43652 Gelation Example 28 Example14

As shown in Table 9, in Example 17 in which unsaturated amide compoundswere prepared by using the composition containing 0.00002 to 2.0 partsby mass of Compound (B) with respect to 100 parts by mass of Compound(A), the unsaturated amide compound 1 having a proper viscosity wasobtained, and the unsaturated amide compound could be prepared withoutany problem.

On the other hand, in Comparative Examples 25 and 26 in whichunsaturated amide compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), although there was no problem inhandling in the stage of raw material, they gelled during thepreparation of the unsaturated amide compounds 2 and 3.

As shown in Table 10, in Example 18 in which unsaturated amide compoundswere prepared by using the composition containing 0.00002 to 2.0 partsby mass of Compound (B) with respect to 100 parts by mass of Compound(A), the unsaturated amide compound 4 having a proper viscosity wasobtained, and the unsaturated amide compound was successfully prepared.

On the other hand, in Comparative Examples 27 and 28 in whichunsaturated amide compounds were prepared by using the compositioncontaining more than 2.0 parts by mass of Compound (B) with respect to100 parts by mass of Compound (A), although there was no problem inhandling in the stage of raw material, they gelled during thepreparation of the unsaturated amide compounds 5 and 6.

<Example 19> (Reaction Product of (Poly)thiol with MOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 177.3 g of 1-octanethiol and 184.3 g of the compositionof Example 4 (The compound (A) is MOI.) were charged and reacted at 80°C. for 24 hours to synthesize an unsaturated thiourethane compound 1.

<Comparative Example 29> (Reaction Product of (Poly)thiol with MOI)

An unsaturated thiourethane compound 2 was synthesized in the samemanner as in Example 19 except that the composition of ComparativeExample 4 (The compound (A) is MOI.) was used in place of thecomposition of Example 4.

<Comparative Example 30> (Reaction of (Poly)thiol with MOI)

An unsaturated thiourethane compound 3 was synthesized in the samemanner as in Example 19 except that the composition of ComparativeExample 6 (The compound (A) is MOI.) was used in place of thecomposition of Example 4.

<Example 20> (Reaction Product of (Poly)thiol with AOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 177.3 g of 1-octanethiol and 167.7 g of the compositionof Example 12 (The compound (A) is AOI.) were charged and reacted at 80°C. for 24 hours to synthesize an unsaturated thiourethane compound 4.

<Comparative Example 31> (Reaction Product of (Poly)thiol with AOI)

An unsaturated thiourethane compound 5 was synthesized in the samemanner as Example 20 except that the composition of Comparative Example9 (The compound (A) is AOI.) was used in place of the composition ofExample 12.

<Comparative Example 32> (Reaction Product of (Poly)thiol with AOI)

An unsaturated thiourethane compound 6 was synthesized in the samemanner as in Example 20 except that the composition of ComparativeExample 13 (The compound (A) is AOI.) was used in place of thecomposition of Example 12.

Viscosities of the reaction liquids containing the unsaturatedthiourethane compounds 1 to 6 obtained in Examples 19 and 20 andComparative Examples 29 to 32 were measured in accordance with JIS-Z8803: 2011 at 25° C. using a tuning fork type vibrating viscometer (SVtype viscometer manufactured by A & D Co., Ltd. (SV −10 Type)). Theresults are shown in Tables 11 and 12.

TABLE 11 Unsaturated Compound B thiourethane Content in Compositioncompound Composition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example19 1 Example 4 489 0.87 Comparative 2 Comparative 28648 Gelation Example29 Example 4 Comparative 3 Comparative 58975 Gelation Example 30 Example6

TABLE 12 Unsaturated Compound B thiourethane Content in Compositioncompound Composition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example20 4 Example 12 597 0.54 Comparative 5 Comparative 26578 GelationExample 31 Example 9 Comparative 6 Comparative 35687 Gelation Example 32Example 13

As shown in Table 11, in Example 19 in which unsaturated thiourethanecompound was prepared by using the composition containing 0.00002 to 2.0parts by mass of Compound (B) with respect to 100 parts by mass ofCompound (A), the unsaturated thiourethane compound 1 having anappropriate viscosity was obtained, and the unsaturated thiourethanecompound was successfully prepared.

On the other hand, in Comparative Examples 29 and 30 in whichunsaturated thiourethane compounds were prepared by using thecompositions containing more than 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A), although therewas no problem in handling in the stage of raw material, the compoundwas gelled during the preparation of the unsaturated thiourethanecompounds 2 and 3.

As shown in Table 12, in Example 20 in which unsaturated thiourethanecompound was prepared by using the composition containing 0.00002 to 2.0parts by mass of Compound (B) with respect to 100 parts by mass ofCompound (A), the unsaturated thiourethane compound 4 having anappropriate viscosity was obtained, and the unsaturated thiourethanecompound was successfully prepared.

On the other hand, in Comparative Examples 31 and 32 in whichunsaturated thiourethane compounds were prepared by using thecompositions containing more than 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A), the unsaturatedthiourethane compounds 5 and 6 were gelatinized during the preparationof the unsaturated thiourethane compounds 5 and 6, although there was noproblem in handling in the raw material stage.

<Example 21> (Reaction Product of Oxime Compound with MOI)

In a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, 167.0 g of 2-butanone oxime (hereinafter also referredto as “MEK oxime”) was charged, and while the temperature was maintainedat 35° C., 293.1 g of the composition of Example 6 (The compound (A) isMOI.) was fed and allowed to react for 2 hours to synthesize MOI-BM(2-butanone oxime-O-(carbamoylethyl-2-methacrylate) as an unsaturatedbutanone oxime compound 1. MOI-BM is a mixture of (2-butanoneoxime-O-(E)-(carbamoylethyl-2-methacrylate) and 2-butanoneoxime-O—(Z)-(carbamoylethyl-2-methacrylate).

Examples of such MOI-BM products include CARENS MOI-BM (registeredtrademark).

<Comparative Example 33> (Reaction Product of Oxime Compound with MOI)

An unsaturated butanone oxime compound 2 was synthesized in the samemanner as in Example 21 except that the composition of ComparativeExample 3 (The compound (A) is MOI.) was used in place of thecomposition of Example 6.

<Comparative Example 34> (Reaction Product of Oxime Compound with MOI)

An unsaturated butanone oxime compound 3 was synthesized in the samemanner as in Example 21 except that the composition of ComparativeExample 7 (The compound (A) is MOI.) was used in place of thecomposition of Example 6.

<Example 22> (Reaction Product of Oxime Compound with AOI)

To a 500 ml four-necked flask equipped with a stirrer, reflux condenserand thermometer, at 15° C., 167.0 g of MEK oxime and 266.7 g of thecomposition of Example 10 (The compound (A) is AOI.) were fed at thesame time and reacted for 1 hour to synthesize AOI-BM (2-butanoneoxime-O-(carbamoylethyl-2-acrylate) as the unsaturated butanone oximecompound 4. AOI-BM is a mixture of 2-butanoneoxime-O-(E)-(carbamoylethyl-2-acrylate) and 2-butanoneoxime-O-(Z)-(carbamoylethyl-2-acrylate).

<Comparative Example 35> (Reaction Product of Oxime Compound with AOI)

An unsaturated butanone oxime compound 5 was synthesized in the samemanner as in Example 22 except that the composition of ComparativeExample 11 (The compound (A) is AOI.) was used in place of thecomposition of Example 10.

<Comparative Example 36> (Reaction Product of Oxime Compound with AOI)

An unsaturated butanone oxime compound 6 was synthesized in the samemanner as in Example 22 except that the composition of ComparativeExample 15 (The compound (A) is AOI.) was used in place of thecomposition of Example 10.

The viscosities of the reaction liquids containing the unsaturatedbutanone oxime compounds 1 to 6, obtained in Examples 21 and 22 andComparative Examples 33 to 36, were measured in accordance with JIS-Z8803: 2011 at 25° C. using a tuning-fork-type vibrating viscometer (SVtype viscometer manufactured by A & D Co., Ltd. (SV-10 Type)). Theresults are shown in Tables 13 and 14.

TABLE 13 Unsaturated Compound B Butanone Oxime Content in Compositioncompound Composition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example21 1 Example 6 623 0.15 Comparative 2 Comparative 24006 Gelation Example33 Example 3 Comparative 3 Comparative 35687 Gelation Example 34 Example7

TABLE 14 Unsaturated Compound B Butanone Oxime Content in Compositioncompound Composition (×10⁻⁴ parts by mass) Viscosity (mPa · sec) Example22 4 Example 10 654 0.22 Comparative 5 Comparative 28674 GelationExample 35 Example 1 Comparative 6 Comparative 37885 Gelation Example 36Example 15

As shown in Table 13, in Example 21, in which unsaturated butanone oximecompounds were prepared by using the composition containing 0.00002 to2.0 parts by mass of the compound (B) with respect to 100 parts by massof the compound (A), the unsaturated butanone oxime compound 1 havingproper viscosity were obtained, and the unsaturated butanone oximecompounds were successfully prepared.

On the other hand, in Comparative Examples 33 and 34 in which anunsaturated butanone oxime compound was prepared by using thecompositions containing more than 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A), although therewas no problem in handling in the stage of raw material, the compoundgelled during the preparation of the unsaturated butanone oximecompounds 2 and 3.

As shown in Table 14, in Example 22, in which unsaturated butanone oximecompounds were prepared by using the composition containing 0.00002 to2.0 parts by mass of the compound (B) with respect to 100 parts by massof the compound (A), the unsaturated butanone oxime compound 4 havingthe proper viscosity were obtained, and the unsaturated butanone oximecompounds were successfully prepared.

On the other hand, in Comparative Examples 35 and 36, in which anunsaturated butanone oxime compound were prepared by using thecomposition containing more than 2.0 parts by mass of the compound (B)with respect to 100 parts by mass of the compound (A), although therewas no problem in handling in the stage of raw material, the compoundgelled during the preparation of the unsaturated butanone oximecompounds 5 and 6.

As shown in the above results, depending on whether or not the contentof the compound (B) with respect to 100 parts by mass of the compound(A) was 0.00002 to 2.0 parts by mass, there was a large difference inthe behavior of the composition during storage. The viscosity of theunsaturated compound obtained by reacting the composition with any oneof (poly)ol, (poly)amine, (poly)carboxylic acid, (poly)thiol and oximecompound also differed greatly depending on whether or not the contentof the compound (B) with respect to 100 parts by mass of the compound(A) in the composition was 0.00002 to 2.0 parts by mass.

From these results, it was confirmed that the concentration of compound(B) in the composition is useful as an index for determining thestability of the composition during storage and as an index fordetermining whether or not a rapid increase in viscosity and/or gelationoccurs during production when the unsaturated compound is produced byusing the composition as a raw material.

INDUSTRIAL APPLICABILITY

According to the present invention, the stability during storage and thestability during transportation of the composition containing theunsaturated isocyanate compound can be improved.

The invention claimed is:
 1. A composition comprising: a compound (A)represented by general formula (1) and a compound (B) represented bygeneral formula (2), wherein the composition comprises 0.00002 to 2.0parts by mass of the compound (B) with respect to 100 parts by mass ofthe compound (A),(R₁—COO)_(n)—R₂—(NCO)_(m)  (1)(R₁—COO)_(n)—R₂—NHC(═O)NH—R₂—(OCO—R₁)_(m)  (2) wherein in the generalformulae (1) and (2), R₁ is an ethylenically unsaturated group having 2to 7 carbon atoms; R₂ is a (m+n)-valent hydrocarbon group having 1 to 7carbon atoms and optionally comprises an ether group; R₁ and R₂ in thegeneral formula (1) are the same as R₁ and R₂ in the general formula(2); and n and m each represent an integer of 1 or
 2. 2. The compositionaccording to claim 1, wherein the compound (A) is at least one compoundselected from the group consisting of 2-methacryloyloxyethyl isocyanate,2-(isocyanatoethyloxy) ethyl methacrylate, 2-acryloyloxyethylisocyanate, 2-(isocyanatoethyloxy) ethyl acrylate, and1,1-bis(acryloyloxymethyl)ethyl isocyanate.
 3. The composition accordingto claim 1, wherein a content of the compound (A) in the composition is95.0% by mass or more.
 4. The composition according to claim 1, whereinthe content of the compound (A) in the composition is 97.0% by mass to99.9% by mass.
 5. The composition according to claim 1, furthercomprising as an additive any one selected from the group consisting ofhydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol,cresol, 2,6-di-tert-butyl-4-methylphenol (BHT), and phenothiazine.
 6. Amethod of producing an unsaturated compound, comprising the steps of:mixing the composition according to claim 1 with a compound havingactive hydrogen; and reacting the compound (A) contained in thecomposition with the compound having active hydrogen to obtain areaction product.
 7. The method of producing an unsaturated compoundaccording to claim 6, wherein the compound having the active hydrogen isan alcohol, a thiol, an amine or a carboxylic acid.
 8. The method ofproducing an unsaturated compound according to claim 6, wherein thereaction product is an unsaturated urethane compound, an unsaturatedthiourethane compound, an unsaturated urea compound, or an unsaturatedamide compound.
 9. The method of producing an unsaturated compoundaccording to claim 6, wherein the reaction product is any one selectedfrom the group consisting of 2-butanoneoxime-O-(carbamoylethyl-2-methacrylate),2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, 2-butanoneoxime-O-(carbamoylethyl-2-acrylate), and2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl acrylate.
 10. The methodof producing an unsaturated compound according to claim 6, wherein areaction temperature at which the compound (A) contained in thecomposition is reacted with the compound having the active hydrogen is−10 to 100° C.